Convertible color transfer



l NOV. 22, 1938. l M, J, PALM, JR 2,137,456

CONVERTIBLE COLOR TRANSFER Filed Dec. 7, 1934 Pff. j,

1 /NI/Em/e MAX J Piz/V, we.

HJM@ SML@ A TTORNE YS' Patented Nov. 22, 14938 UNITED STATESCGNVERTIBLE- COLOR TRANSFER Max J. Palm, Jr., Cincinnati, Ohio,assi'gnor to The Palm Bros. Decalcomania Co., Cincinnati, Ohio, acorporation of Ohio Application December 7, 1934, Serial No. 756,484

in particular, to the use of materials in the decal comanias which canbe utilized, upon the application of a suitable temperature or moisturecondition, to indicate whether the decalcomania is a genuine one or not.

It is the object of this invention to provide a stamp, label, wrapper orother form in a decalcomania or in any similar device which, when heator moisture is applied, the device will change color and therebyindicate that it is of genuine manufacture. In the field of stamps andlabels for Government tax purposes, it is diflifcult to detectcounterfeits. The purpose of the use of a thermal color or a color whichis changed upon the application of moisture permits of such anidentification by the change of color upon such application.

It is a further object to provide a stamp, such as a stamp or label forcigarette packages and the like, in which the application of such heatas from a lighted cigarette, when brought close to the stamp or labelwill cause it to change color, as from yellow to red, or from red tobrown, or any other color combination depending upon the chemicalsemployed.

This invention isbroadly for incorporating ,a material in the glue,paper or printing of a stamp, label, or the like, so that, upon theapplication of the testing material, temperature or moisture, thearticle in question will change color to identify it as genuine.

Referring to the drawing:

Figure 1 is a perspective of a slide-oli decalcomania, partially brokenaway, embodying the invention described herein;

Figure 2 is a section on the line 2 2 of Figure 1;

Figure 3 is a view similar to Figure 1 of a regular decalcomania turnedback to show the arrangement of the layers; it will be understood thatthis view is greatly exaggerated and that no attempt to duplicate theexact thicknesses or relative proportions of the several layers has beenmade;

Figure 4 is a section on the line 4-4 of Fig-i ure 3.

Referring to the drawing in detail, and in par-'- ticular to Figures 1and 2 showing a slide-off decalcomania, l represents the paper base, 2the soluble glue, 3 the white coats, 4 the color coats, i the varnishcoat, and 6 the coat which changes upon the application of somepredetermined external condition, such as heat. 'Ihis coat 6 may beinterposed at any place and between any layers but, for the purpose ofillustration, it has been shown on top of the face of the decalcomania.According to the usual practice, the layers 3, 4, 5 and 6, upon thebringing of the layer 2 into the solution, are slid'off as a body on tosome supporting surface, such as a cigarette package, bottle and thelike.

Referring to Figures 3 and 4, particularly where there is shown theregular type decalcomania that is applied to the surface by varnish andthen the paper backing is removed after being moistened, 1 indicates asurface to which the decalcomania is to be applied. This may be a papercontainer, such as a cigarette package cover. The next layer to thesupport 1 is the varnish layer 8. The decalcomania proper consists ofthe leaf or bronze or color layer 9, then the layer of White ink, orleaf or bronze i0 on which is printed the color' layer Il and on top ofthis is the layer i2 which changes color under heat, moisture and thelike. On this is the glue layer that is solvent in water and whichsupports the paper cover. This glue layer is designated i3 and the papercover i4.

In making the decalcomania transfer of the regular type, the so-calledchange color or thermal color can be printed in a design or completelayer and can be printed at any place' between any of the layersconstituting the decalcomania. The material should be susceptible ofbeing printed as an ordinary printing coat like the ink coats areprinted to form the decalcomania. It is, therefore, very thin but it isreadily susceptible according to its chemical composition to heat ormoisture, or it may be susceptible to some chemical test as by theapplication of sodium silicate.

As typical examples of the material to be used, without confining myselfto particular materials, I have found that the following examples aresatisfactory:

Exmu: 1

Silver mercuric iodide I provide a mixture of mercury, silver and iodinewith suitable re-agents in order to produce the double, iodides ofmercury and silver, giving a yellow color that turns to red upon theapplication of heat, such as the heat from a lighted cigarette, and willreturn to yellow upon cooling.

This compound is best prepared by precipitating from a solution ofpotassium mercuric iodide with silver nitrate. It is a yellow insolublecompoundvwhich changes to an orange-red color on gentlyl heating andreturns to its original color on cooling.

double iodides of mercury and copper. cooled this gives aV red colorthat, upon being By using approximately the theoretical quantities ofeach chemical required the best yield is obtained. For example, 80 gramsof mercurio chloride are dissolved in a suitable quantity of water, sayone liter, and to this are added slowly. with stirring, 20ilv grams ofpotassium iodide dissolved in another liter of water. At ilrst a brightred precipitate is formed which should be completely re-dissolved whenall oi the potassium iodide has been added. In a third liter of waterare dissolved 100 grams of silver nitrate and this solution is addedslowly and with stirring to the above solution. The yellowprecipitateformed is silver mercurio iodide which is illtered oil andwashed with water thoroughly before drying.

Exaurnl' 2 Copper mercuric iodide I provide a mixture of mercury, copperand iodine with suitable reagents to produce the subjected to heat,turns to black-brown, and upon cooling, returns to red.

This is prepared in a similar manner to the silver mercuriciodideexcepting copper sulphate is used in place of the silver nitrate.

I .To prepare it 110 grams oi mercurio chloridev are dissolved in oneliter of water and to this are added 2'10 grams oi! potassium iodidedissolved in another liter of water. The red precipitate formed at ilrstshould be completely dissolved when all of the potassium iodide has beenadded. To this solution is added a solution of 100 grams of coppersulphate in one liter of water. The red precipitate formed is coppermercurio iodide. This should be filtered oil' and washed ilrst with adilute solution of 'sodium thiosulphate until all traces of iodine areremoved and then washed vith water. The precipitate .wher` dried isready or use. Y

Copper mercurio iodide is a bright red com pound changingto a deepchocolate brown color .on heating, and returning to its original coloron cooling.

A Exnn'r.: 3

Hercurc `iodide its original color on cooling. However, if it isrubbedthe red color is restored instantly.

To prepare it 100 grams of mercuric chloride:

dissolved in about one liter of water, and to this added a solution of122 grams of potassium iodide also in one liter of water'. The redprecipitate is filtered on and washed thoroughly with water and thendried. Exam! 4 If desired, there can be incorporated in the printing inkthe intermediates used for producing the resulting dye stuff, which whenbrought together in a suitable medium, form a dye. For instance,betanaphthol is placed in the ink and if .it is tested withparanitraniline a red dye will be produced, which gives para red. Noheat is necessary for this change.

When

Dry phenolphthalein and dry sodium carbonate can be placed in the inkand upon moisture being added a red color results from the reaction o!the water on the phenolphthalein and the sodium carbonate. If desired,one of these elements can be mixed in the ink and then the printingtreated with a solution of the other, in the presence oi moisture, toget the same result.

I Exnlrx.: 6

Exnlru'l.

Cobalt chloride can be employed in the deca comania and, upon theapplication of sodium silicate, it will change any color.

. Exslll I.: 8 Calcium oxide when lmoistened will turn pink litmus paperblue; ferric ammonium sulphate solution when treated with sodiumsilicate turns red to brown. Manganese sulphate solution when treatedwith sodium silicate turns pink. VSodium carbonate when treated withwater and nickel ammonium sulphate solution will turn a light green.

In preparing these compounds all equipment must be made of glass,porcelain, nickel, Monel metal. stainless steel, or chromium plated toprevent discoloration anddecomposition of the compounds.

In the preparation of the copper mercuric iodide free iodine is producedas a by-product of the reaction. This is due to the reduction of thelcupric salt to the cuprous state. It is possible that this may beavoided by reducing the cupric salt with some reducing agentbeforereacting with the iodide and thus increasing the yield of the color.

If these compounds are to be ground with oils or varnish it is possiblethat special vehicles will be required to prevent discoloration of thecolor. Also, some substitute, may be'required for the usual metallicdriers as these may likewise cause discoloration. Vehicles of thesynthetic lacquer type will prove satisfactory.

It will be understood that it is desired to comprehend within thisinvention such modifications as may be necessary to adapt it to varyingconditions and uses. r

By the use of the words "suitable reagent in the following claims Iintend to comprehend the application of heat, moisture or a suitablechemical to bring about the desired color change.

Having thus fully described this invention, what is claimed as new andis desired to secure by Letters Patent, is:

1. A new article of manufacture for use as a decalcomania comprisinglayers of printing ink to form the decalcomania, and an area of athermal color which will change its color upon the application of heat.

2. A new article of manufacture for use as a decalcomania comprising adecalcomania body consisting of layers of printing ink, and a printedarea of a `thermal color that will change its color temporarily upon theapplication of heat.

3. A new article ofmanufacture for use as a decalcomania comprising adecalcomania body consisting oi' layers of printing ink, and a print- 75ed area of a thermal color that will change its color temporarily uponthe application of moisture.

4. A new article of manufacture for use as a decalcomania comprising adecalcomania body consisting of layers of printing ink, and a printedarea of a thermal color that will change its l Adouble iodides ofmercury and silver.

6. A new article of manufacture for use as a decalcomania comprising aprinted decalcomania having printed therewith a temporarily changingthermal color, such as a mixture of mercury, silver and iodineconstituting a mixture of the double iodides of mercury and silver butwith such reagents as will produce such change in color.

7. A new article of manufacture for use as a decalcomania comprising aprinted decalcomania having printed therewith a temporarily changingthermal color, such as a mixture of mercury, copper and iodineconstituting a mixture of the double iodides of mercury and copper.

8. A new article of manufacture for use as a decalcornania labelcomprising a printed decalcomania having printed therewith a thermalcolorthat, upon the application of heat, changes from yellow to red and,upon cooling, returns to yellow.

9. A new article of manufacture for use as a decalcomania comprising adecalcomania printed from ink, and a thermal color printed therewithadapted, upon the application of heat, to change permanently its color.

10. A new article of manufacture for use as a. decalcomania comprising adecalcomania printed from ink, and a thermal color printed therewithadapted, upon the application of heat, to

change permanentlyits color, such as from red

